Adhesion promoter

ABSTRACT

Compositions useful for improving the adhesion of coating compositions, such as dielectric film-forming compositions, include a hydrolyzed poly(alkoxysilane). These compositions are useful in methods of improving the adhesion of coating compositions to a substrate.

This application is a Divisional of U.S. patent application Ser. No.14/062,677, filed on Oct. 24, 2013, which is a Continuation-in-Part ofU.S. Non-Provisional application Ser. No. 13/664,337, filed on Oct. 30,2012.

The present invention relates to the field of coating compositions andmore particularly to a solution for improving the adhesion of certaincoating compositions to a substrate.

Coating compositions are widely used in the electronics industry todeposit various organic-containing materials, such as polymericmaterials, on a variety of substrates. Often the substrates areinorganic or have inorganic areas on the surface to be coated. Forexample, coating compositions such as dielectric film-formingcompositions and bonding or adhesive compositions are often applied toglass, metal surfaces, and/or semiconductor surfaces such as silicon,gallium-arsenide, and silicon-germanium. Many organic materials do notadhere well to substrates having inorganic surfaces because they do notcontain groups that have an affinity for such surfaces. Accordingly, itis common practice to treat such substrate surfaces with an adhesionpromoter prior to disposing an organic-containing coating composition onit. Silanes are among the more common adhesion promoters usedindustrially.

Arylcyclobutene-based materials have been used in a wide variety ofapplications in the electronics industry due to their superiordielectric properties, excellent gap-fill and planarization, and lowmoisture adsorption. To use arylcyclobutene materials in applicationssuch as interlevel dielectrics and wafer bonding applications, adequateadhesion of the arylcyclobutene material to various substrates (such assilicon, silicon nitride, gold, and copper) is required. Arylcyclobutenematerials by themselves do not possess sufficient adhesion to thesesubstrates, and therefore, an adhesion promoter is usually applied toenhance adhesion prior to coating the arylcyclobutene material.

Various adhesion promoters are known for use with arylcyclobutenes. Forexample, U.S. Pat. No. 5,668,210 discloses certain alkoxysilanes asadhesion promoters for arylcyclobutenes. Only monosilanes are disclosedin this patent. These alkoxysilanes are hydrolyzed with 10 to 80% of thestoichiometric amount (that is mole %) of water. However, conventionaladhesion promoters are not able to meet the increasing requirements ofthe electronics industry for smaller feature sizes (<10 μm) and morecomplex chip designs, often resulting in delamination or other adhesivefailures.

There remains a need for adhesion promoters that enable the use ofarylcyclobutanes, as well as other organic coatings, with smallerfeature sizes (<10 μm) and more complex chip designs. The presentinvention addresses one or more of these deficiencies.

The present invention provides a process of manufacturing a device,comprising: providing a device substrate having a surface to be coated;treating the surface to be coated with an adhesion promoting compositioncomprising an poly(alkoxysilane) and a solvent, wherein thepoly(alkoxysilane) is hydrolyzed with ≦1 mole % of water, and whereinthe composition comprises ≦1 mole % of alcohol of hydrolysis; anddisposing a coating composition comprising an oligomer chosen frompolyarylene oligomers, poly(cyclic-olefin) oligomers, arylcyclobuteneoligomers, vinyl aromatic oligomers, and mixtures thereof on the treatedsurface. It is preferred that the device substrate is an electronicdevice substrate.

Also provided by the present invention is an adhesion promotingcomposition comprising: an oligomer chosen from polyarylene oligomers,poly(cyclic-olefin) oligomers, arylcyclobutene oligomers, and mixturesthereof; a poly(alkoxysilane) hydrolyzed with ≦1 mole % of water; and asolvent; wherein the composition comprises ≦1 mole % of alcohol ofhydrolysis. Preferably, the composition has a mean particle size ≦1 nmas determined by dynamic light scattering.

Further, the present invention provides a method of manufacturing adevice, comprising: providing a device substrate having a surface to becoated; and depositing a composition comprising: an oligomer chosen frompolyarylene oligomers, poly(cyclic-olefin) oligomers, arylcyclobuteneoligomers, vinyl aromatic oligomers, and mixtures thereof; andpoly(alkoxysilane) hydrolyzed with ≦1 mole % of water; and a solvent;wherein the composition comprises ≦1 mole % of alcohol of hydrolysis.

It has been surprisingly found that poly(alkoxysilanes) hydrolyzed with≦1 mole % of water are particularly effective adhesion promoters forcoating oligomers chosen from polyarylene oligomers, poly(cyclic-olefin)oligomers, arylcyclobutene oligomers, vinyl aromatic oligomers, andmixtures thereof used in the manufacture of electronic devices. Suchcoating oligomers are useful in preparing dielectric coatings,photodefinable coatings, temporary bonding adhesives, and permanentbonding adhesives, among other applications.

As used throughout this specification, the following abbreviations shallhave the following meanings, unless the context clearly indicatesotherwise: ° C.=degrees Celsius; g=grams; L=liter; mL=milliliters;ppm=parts per million; mm=millimeters; μm=micron=micrometers;nm=nanometers; and A=angstroms. “Wt %” refers to percent by weight,based on the total weight of a referenced composition, unless otherwisenoted. All amounts are percent by weight and all ratios are molarratios, unless otherwise noted. All numerical ranges are inclusive andcombinable in any order, except where it is clear that such numericalranges are constrained to add up to 100%. The articles “a”, “an” and“the” refer to the singular and the plural.

As used throughout the specification, “feature” refers to the geometrieson a substrate, and particularly on a semiconductive wafer. The term“alkyl” includes linear, branched and cyclic alkyl. Likewise, “alkenyl”refers to linear, branched and cyclic alkenyl. “Aryl” refers to aromaticcarbocycles and aromatic heterocycles. The term “oligomer” refers todimers, trimers, tetramers and other relatively low molecular weightmaterials that are capable of further curing. By the term “curing” ismeant any process, such as polymerization or condensation, thatincreases the molecular weight of a material or composition.

The poly(alkoxysilanes) useful in the present invention are composed ofat least two alkoxysilane moieties, that is, moieties represented by—Si(Z)₂OR¹. Preferably, the poly(alkoxysilanes) have from 2 to 6alkoxysilane moieties, more preferably from 2 to 4 alkoxysilanemoieties, even more preferably from 2 to 3 alkoxysilane moieties; andmost preferably 2 alkoxysilane moieties. As used herein, the term“alkoxysilane” moiety includes silane moieties substituted with one ormore (C₁-C₆)alkoxy groups and/or one or more (C₁-C₆)acyloxy groups.Preferably, each alkoxysilane moiety comprises three (C₁-C₆)alkoxygroups and/or (C₁-C₆)acyloxy groups, and more preferably three(C₁-C₆)alkoxy groups.

Particularly preferred poly(alkoxysilanes) prior to being hydrolyzedhave the formula:

wherein each R is independently chosen from (C₁-C₆)alkylidene,(C₁-C₆)alkylene, (C₆-C₁₀)arylene, and (C₂-C₆)alkenylene; each R¹ isindependently chosen from H, (C₁-C₆)alkyl and (C₁-C₆)acyl; each Z isindependently chosen from (C₁-C₆)alkyl, (C₂-C₆)alkenyl and —OR¹;X═(C₆-C₁₀)arylene, O, S, S—S, S—S—S, S—S—S—S, N(Y), P(Y) or a covalentbond; Y═H, (C₁-C₆)alkyl, (C₁-C₆)alkylene-N(Y¹)₂, (C₂-C₆)alkenyl,(C₁-C₆)alkylene-Si(Z)₂(OR¹), (C₁-C₆)alkylidene-Si(Z)₂(OR¹), oraryl(meth)acryloyl; and Y¹═H, (C₁-C₆)alkyl, or (C₂-C₆)alkenyl; whereineach R is optionally substituted with one or more of(C₁-C₆)alkylidene-Si(Z)₂(OR¹) and (C₁-C₆)alkylene-Si(Z)₂(OR¹). Each R ispreferably independently chosen from (C₁-C₆)alkylidene, (C₁-C₆)alkylene,and (C₂-C₆)alkenylene, each optionally substituted with one or more of(C₁-C₆)alkylidene-Si(Z)₂(OR¹) and (C₁-C₆)alkylene-Si(Z)₂(OR¹). Morepreferably, each R is independently chosen from (C₂-C₆)alkylidene,(C₂-C₆)alkylene, and (C₂-C₆)alkenylene. When an R group is substitutedwith (C₁-C₆)alkylidene-Si(Z)₂(OR¹) or (C₁-C₆)alkylene-Si(Z)₂(OR¹), it ispreferred that 1 to 2 of such groups are present. Each R¹ is preferablychosen from (C₁-C₄)alkyl and (C₂-C₆)acyl; and more preferably from(C₁-C₃)alkyl and (C₂-C₄)acyl. It is preferred that each Z is chosen from(C₁-C₄)alkyl, (C₂-C₆)alkenyl and —OR¹; and more preferably each Z is—OR¹. Preferably, X is chosen from S—S, S—S—S, S—S—S—S, N(Y), or acovalent bond, and more preferably from N(Y) or a covalent bond. It ispreferred that Y is chosen from H, (C₁-C₄)alkyl, (C₁-C₄)alkylene-N(Y¹)₂,(C₂-C₆)alkenyl, (C₂-C₆)alkylene-Si(Z)₂(OR¹), and aryl(meth)acryloyl; andmore preferably from H, (C₂-C₄)alkylene-N(Y¹)₂, (C₂-C₄)alkenyl,(C₂-C₄)alkylene-Si(Z)₂(OR¹), and aryl(meth)acryloyl. Y¹ is preferablychosen from H, (C₁-C₄)alkyl, or (C₂-C₄)alkenyl; and more preferably fromH, and (C₁-C₄)alkyl. Suitable poly(alkoxysilanes) are commerciallyavailable from a variety of sources, such as Sigma-Aldrich (St. Louis,Mo.), or may be prepared by any suitable method known in the literature.The poly(alkoxysilanes) may be used without further purification, or maybe purified using suitable conventional procedures.

Conventional alkoxysilane adhesion promoters use a large amount of water(close to a stoichiometric amount) to partially or fully hydrolyze thealkoxysilanes. To achieve complete (100%) hydrolysis, a stoichiometricamount of water is 1 molar equivalent of water for each molar equivalentof alkoxy (or acyloxy) group present on each alkoxysilane moiety. Inpractice, somewhat less than a stoichiometric amount of water isrequired for complete hydrolysis since water is formed by condensationreactions during the hydrolysis. Accordingly, conventional adhesionpromoters typically use from 10 to 80% of the stoichiometric amount ofwater. In comparison, the poly(alkoxysilanes) of the present inventionare partially hydrolyzed using very small amounts of water, that is muchless than a stoichiometric amount of water. To be useful in the presentinvention, the poly(alkoxysilanes) are hydrolyzed with ≦1 mole % ofwater, preferably ≦0.5 mole %, and more preferably ≦0.3 mole %. Asuitable amount of water for such hydrolysis is from 0.0001 to 1 mole %,preferably from 0.001 to 1 mole %, more preferably from 0.001 to 0.5mole %, even more preferably from 0.01 to 0.5 mole %. The water used inthe hydrolysis should be purified, and preferably is deionized. As aresult of this hydrolysis, an alcohol of hydrolysis is formed, which isthe alcohol formed from cleavage of an alkoxy group from the silanemoiety. For example, cleavage of an ethoxy group from a triethoxysilanemoiety results in the formation of ethanol as the alcohol of hydrolysis.As a further example, hydrolysis of a triacetoxysilane moiety results inthe formation of acetic acid as the “alcohol” of hydrolysis. The amountof alcohol of hydrolysis resulting from the present poly(alkoxysilane)hydrolysis is ≦1 mole %, preferably ≦0.5 mole %, and more preferably≦0.3 mole %.

The poly(alkoxysilanes) may be hydrolyzed according to procedures knownin the art, such as where the poly(alkoxysilane) is contacted with adesired amount of water, or by contacting the poly(alkoxysilane) withwater in the presence of a volatile solvent, or by simply combining thepoly(alkoxysilane) with a suitable solvent where the solvent hassufficient residual water content to effect the desired level ofhydrolysis. If a volatile solvent (or solvent mixture) is used, it isoptionally removed prior to the hydrolyzed poly(alkoxysilane) beingincorporated into the present coating composition. In one preferredprocess, the hydrolysis is performed by combining the poly(alkoxysilane)with a suitable organic solvent having sufficient residual water toeffect the desired level of hydrolysis. In another preferred process, adesired amount of water is first combined with a desired solvent, andthen this mixture is combined with the poly(alkoxysilane). Optionally,an acidic or basic catalyst may be employed in the hydrolysis reaction,but it is preferred that no catalyst be used.

The optional acidic or basic catalysts may be any acidic or basiccompound which will catalyze the hydrolysis of the poly(alkoxysilane).Examples of acidic catalysts include but are not limited to nitric acid,hydrochloric acid, sulfuric acid, trifluoroacetic acid, chloroaceticacid, methane sulfonic acid, and phosphoric acid. Examples of basiccatalysts include but are not limited to potassium hydroxide, sodiumhydroxide, ammonium hydroxide, tetramethylammonium hydroxide, andtetraethylammonium hydroxide. When present, the catalyst is used inamounts sufficient to catalyze the hydrolysis reaction. The amount ofcatalyst advantageously employed will depend upon a number of factorsincluding the desired rate of hydrolysis, the catalyst, thepoly(alkoxysilane) used, and the degree of hydrolysis desired.Preferably, the catalyst is present in amounts from 0 ppm to 50 ppmbased on the amount of poly(alkoxysilane). More preferably, the catalystis present in amounts from 0 ppm to 100 ppm and most preferably from 0ppm to 30 ppm, based on the amount of poly(alkoxysilane).

While not wishing to be bound by theory, it is believed that hydrolysisof poly(alkoxysilanes) produces a mixture of nonhydrolyzed, partiallyhydrolyzed, fully hydrolyzed and oligomerized poly(alkoxysilanes).Oligomerization occurs when a hydrolyzed or partially hydrolyzedpoly(alkoxysilane) reacts with another poly(alkoxysilane) to producewater and an Si—O—Si bond. As used herein, the term “hydrolyzedpoly(alkoxysilane)” encompasses all level of hydrolysis of thepoly(alkoxysilane), as well as oligomerized poly(alkoxysilane). Also asused herein, the term “poly(alkoxysilane) and/or hydrolyzedpoly(alkoxysilane)” refers to a poly(alkoxysilane), or a hydrolyzedpoly(alkoxysilane), or a mixture of these.

In the hydrolysis reaction, the poly(alkoxysilane), water, solvent, andoptional catalyst are mixed until the desired hydrolysis is complete.While the time to complete the hydrolysis will vary depending on anumber of factors, including the specific reactants employed and thelevel of hydrolysis desired, in general, the hydrolysis is complete in 2minutes to 5 hours, preferably from 4 minutes to 2 hours, and morepreferably from 10 minutes to 1 hour. In general, because of the verylow levels of water used, the poly(alkoxysilane), water, and solventwill form a single-phase mixture. In general, the mixture is agitatedfor 1 minute to 2 hours after a single phase is obtained to complete thehydrolysis reaction. The temperature at which hydrolysis is conducted ispreferably from about 15 to 100° C., more preferably from 20 to 50° C.,and most preferably from 20 to 25° C. Hydrolysis rates increase withincreasing temperatures. Preferably, the hydrolysis is conducted in theabsence of a catalyst. In such procedure, the desired amount of water ismixed with the desired solvent, then combined with thepoly(alkoxysilane) and stirred for a sufficient period of time for thedesired extent of hydrolysis to occur. Preferably, the solvent used isthe same solvent used to prepare the treating (adhesion promoter)composition. This method may take up to several days dependent upon thepoly(alkoxysilane) and the temperature at which hydrolysis occurs. Insome applications this method may be preferred when residual catalystlevels have an adverse effect on subsequent use of thepoly(alkoxysilane).

The present adhesion promoter compositions comprise a poly(alkoxysilane)hydrolyzed with ≦1 mole % of water and a solvent; wherein thecomposition comprises ≦1 mole % of alcohol of hydrolysis. The solventused in the adhesion promoting composition of the present invention canbe any single organic solvent or mixture of two or more organic solventsin which the hydrolyzed poly(alkoxysilane) is soluble. Exemplary organicsolvents include, without limitation: aromatic hydrocarbons such astoluene, xylene, mesitylene and alkylnaphthalenes; alcohols such as2-methyl-1-butanol, 4-methyl-2-pentanol, and methyl isobutyl carbinol;esters such as ethyl lactate, propylene glycol methyl ether acetate(PGMEA), and methyl 2-hydroxyisobutyrate; lactones such asgamma-butyrolactone; lactams such as N-methylpyrrolidinone; ethers suchas anisole, propylene glycol methyl ether and dipropylene glycoldimethyl ether isomers (commercially available from The Dow ChemicalCompany as Proglyde™ DMM); ketones such as cyclohexanone andmethylcyclohexanone; and mixtures thereof.

In general, the present adhesion promoter compositions comprise from0.01 to 10 wt % of poly(alkoxysilane) and/or hydrolyzedpoly(alkoxysilane), and from 90 to 99.99 wt % of solvent. Preferably,the adhesion promoter compositions comprise form 0.01 to 5 wt % ofpoly(alkoxysilane) and/or hydrolyzed poly(alkoxysilane), more preferablyfrom 0.01 to 3 wt %, and even more preferably from 0.01 to 2 wt %.Preferably, the adhesion promoter compositions comprise from 90 to 99.95wt % of solvent, more preferably from 95 to 99.95 wt %, and even morepreferably from 98 to 99.9 wt %. Particularly preferred compositionscomprise from 0.05 to 3 wt % of poly(alkoxysilane) and/or hydrolyzedpoly(alkoxysilane), and from 97 to 99.95 wt % of solvent.

The present adhesion promoter compositions are typically applied to anelectronic device substrate to improve the adhesion of subsequentlyapplied coating compositions. The present process of manufacturing adevice, comprises: providing a device substrate having a surface to becoated; treating the surface to be coated with a composition comprisingan poly(alkoxysilane) and a solvent, wherein the poly(alkoxysilane) ishydrolyzed with ≦1 mole % of water, and wherein the compositioncomprises ≦1 mole % of alcohol of hydrolysis; and disposing acomposition comprising an oligomer chosen from polyarylene oligomers,poly(cyclic-olefin) oligomers, arylcyclobutene oligomers, vinyl aromaticoligomers, and mixtures thereof on the treated surface.

The device may be any suitable substrate used in the manufacture ofelectronic devices, including, without limitation: packaging substratessuch as multichip modules; flat panel display substrates; integratedcircuit substrates, substrates for light emitting diodes (LEDs),semiconductor wafers, polycrystalline silicon substrates, and the like.Exemplary device substrates which can be coated with the coatingcomposition include metals such as aluminum, copper, gold, silver,titanium, tantalum, nickel, tin, tin-alloys, and the like; ceramics suchas alumina, silica, sapphire, MgO, BeO, including spinels, aluminumnitride, boron nitride, silicon nitride, silicon carbide, and galliumarsenide; glass such as fiber glass, lime glass, flint glass,borosilicate glass, GORILLA™ glass, PYREX™ glass and VYCOR™ glass; andsemiconductor wafers. A wide variety of semiconductor wafers may beemployed in the present invention. As used herein, the term“semiconductor wafer” is intended to encompass “an electronic devicesubstrate,” “a semiconductor substrate,” “a semiconductor device,” andvarious packages for various levels of interconnection, including asingle-chip wafer, multiple-chip wafer, packages for various levels, orother assemblies requiring solder connections. Particularly suitablesubstrates are patterned wafers, such as patterned silicon wafers andpatterned gallium-arsenide wafers. Such wafers may be any suitable size.Preferred wafer diameters are 200 mm to 300 mm, although wafers havingsmaller and larger diameters may be suitably employed according to thepresent invention. As used herein, the term “semiconductive substrates”includes any substrate having one or more semiconductor layers orstructures which include active or operable portions of semiconductordevices. The term “semiconductor substrate” is defined to mean anyconstruction comprising semiconductive material, including but notlimited to bulk semiconductive material such as a semiconductive wafer,either alone or in assemblies comprising other materials thereon, andsemiconductive material layers, either alone or in assemblies comprisingother materials. A semiconductor device refers to a semiconductorsubstrate upon which at least one microelectronic device has been or isbeing batch fabricated. Preferably, if the substrate is a metal such ascopper, it is treated with an etchant such as 1% acetic acid prior toapplication of the coating composition. Substrates commonly used in highdensity electronic circuitry, such as silicon, thermally oxidizedsilicon, GaAs, alumina and aluminum are commonly treated by processessuch as oxygen plasma etching or RCA clean, to control surfacechemistry.

The device substrate surface is treated by contacting the devicesubstrate surface with the present adhesion promoter composition usingany suitable method. Exemplary methods well-known in the art include,without limitation, spin-coating, curtain coating, spray coating, rollercoating, dip coating, and screen printing, among other methods. In thesemiconductor manufacturing industry, spin-coating is preferred to takeadvantage of existing equipment and processes. Preferably, after beingdisposed on a surface, the solvent is removed prior to the next step.Solvent removal is typically achieved by heating (baking) the substrate,such as by heating at a temperature of 80 to 180° C. for a period oftime, such as from 10 to 600 seconds.

After contacting the device substrate with the adhesion promotercomposition, a coating composition comprising an oligomer chosen frompolyarylene oligomers, poly(cyclic-olefin) oligomers, arylcyclobuteneoligomers, vinyl aromatic oligomers, and mixtures thereof is disposed onthe treated surface. Such composition may be disposed on the substrateusing any of the above-described methods for disposing the adhesionpromoter on the substrate. Typically, the coating composition comprisesone or more oligomers, one or more organic solvents, and optionally oneor more additional components such as curing agents, coating enhancers,and the like.

A wide variety of polyarylene oligomers may be used in the presentinvention. As used herein, the term “polyarylenes” includes polyaryleneethers. Suitable polyarylene oligomers may be synthesized fromprecursors such as ethynyl aromatic compounds of the formula:

wherein each Ar is an aromatic group or inertly-substituted aromaticgroup: each R² is independently hydrogen, an alkyl, aryl orinertly-substituted alkyl or aryl group; L is a covalent bond or a groupwhich links one Ar to at least one other Ar; n and m are integers of atleast 2; and q is an integer of at least 1. As such, the ethynylaromatic compounds typically have four or more ethynyl groups (forexample, tetraethynyl aromatic compounds).

Suitable polyarylene oligomers used in the temporary bondingcompositions may comprise a polymer comprising as polymerized units:

wherein Ar′ is the residual of the reaction of product of (C≡C)_(n)—Aror Ar—(C≡C)_(m) moieties and R², L, n and m are as defined above.Polyarylene copolymers useful in the invention include as polymerizedunits a monomer having the formula:

wherein Ar′ and R² are as defined above.

Exemplary polyarylenes include, but are not limited to, those whereinAr-L-Ar is: biphenyl; 2,2-diphenyl propane; 9,9′-diphenyl fluorene;2,2-diphenyl hexafluoro propane; diphenyl sulfide; oxydiphenylene;diphenyl ether; bis(phenylene)diphenylsilane; bis(phenylene) phosphineoxide; bis(phenylene)benzene; bis(phenylene)naphthalene;bis(phenylene)anthracene; thiodiphenylene; 1,1,1-triphenyleneethane;1,3,5-triphenylenebenzene; 1,3,5-(2-phenylene-2-propyl)benzene;1,1,1-triphenylenemethane; 1,1,2,2-tetraphenylene-1,2-diphenylethane;bis(1,1-diphenyleneethyl)benzene;2,2′-diphenylene-1,1,1,3,3,3-hexafluoropropane;1,1-diphenylene-1-phenylethane; naphthalene; anthracene; orbis(phenylene)napthacene; more preferably biphenylene; naphthylene;p,p′-(2,2-diphenylene propane) (or —C₆H₄—C(CH₃)₂—C₆H₄—);p,p′-(2,2-diphenylene-1,1,1,3,3,3hexafluoropropene) and(—C₆H₄—C(CF₃)₂—C₆H₄—). Useful bis-phenyl derivatives include2,2-diphenyl propane; 9,9′-diphenyl fluorene; 2,2-diphenyl hexafluoropropane; diphenyl sulfide; diphenyl ether; bis(phenylene)diphenylsilane;bis(phenylene)phosphine oxide; bis(phenylene)benzene;bis(phenylene)naphthalene; bis(phenylene)anthracene; orbis(phenylene)napthacene.

The polyarylene precursor monomers may be prepared by a variety ofmethods known in the art, such as by: (a) selectively halogenating,preferably brominating, a polyphenol (preferably a bisphenol) preferablyin a solvent, where each phenolic ring is halogenated with one halogenon one of the two positions ortho to the phenolic hydroxyl group; (b)converting the phenolic hydroxyl on the resultingpoly(ortho-halophenol), preferably in a solvent, to a leaving group suchas a sulfonate ester (for example, a trifluoromethanesulfonate esterprepared from trifluoromethanesulfonyl halide or trifluoromethanesulfonic acid anhydride) which is reactive with and replaced by terminalethynyl compounds; and (c) reacting the reaction product of step (b)with an ethynyl-containing compound or an ethynyl synthon in thepresence of an aryl ethynylation, preferably palladium, catalyst and anacid acceptor to simultaneously replace the halogen and thetrifluoromethylsulfonate with an ethynyl-containing group (for example,acetylene, phenylacetylene, substituted phenylacetylene or substitutedacetylene). Further explanation of this synthesis is provided in Int.Pat. App. WO 97/10193 (Babb).

The ethynyl aromatic monomers of Formula (I) are useful to preparepolymers of either Formula (II) or (III). Polymerization of the ethynylaromatic monomers is well within the ability of one skilled in the art.While the specific conditions of polymerization are dependent on avariety of factors including the specific ethynyl aromatic monomer(s)being polymerized and the desired properties of the resulting polymer,in general, the conditions of polymerization are detailed in Int. Pat.App. WO 97/10193 (Babb).

Particularly suitable polyarylenes for use in the present inventioninclude those sold as SiLK™ Semiconductor Dielectric (available from DowElectronic Materials, Marlborough, Mass.). Other particularly suitablepolyarylenes include those disclosed in WO 00/31183, WO 98/11149, WO97/10193, WO 91/09081, EP 755 957, and U.S. Pat. Nos. 5,115,082;5,155,175; 5,179,188; 5,874,516; and 6,093,636.

Suitable cyclic-olefin materials are poly(cyclic-olefins), which may bethermoplastic, and preferably have a weight average molecular weight(M_(w)) of from 2000 to 200,000 Daltons, more preferably from 5000 to100,000 Daltons, and even more preferably from 2000 to 50,000 Daltons.Preferred poly(cyclic-olefins) have a softening temperature (meltviscosity at 3,000 PaS) of at least 100° C., and more preferably atleast 140° C. Suitable poly(cyclic-olefins) also preferably have a glasstransition temperature (T_(g)) of at least 60° C., more preferably from60 to 200° C., and most preferably from 75 to 160° C.

Preferred poly(cyclic-olefins) are comprised of recurring monomers ofcyclic-olefins and acyclic olefins, or ring-opening polymers based oncyclic-olefins. Suitable cyclic olefins for use in the present inventionare chosen from norbornene-based olefins, tetracyclododecene-basedolefins, dicyclopentadiene-based olefins, and derivatives thereof.Derivatives include alkyl (preferably C₁-C₂₀ alkyls, more preferablyC₁-C₁₀ alkyls), alkylidene (preferably C₁-C₂₀ alkylidenes, morepreferably C₁-C₁₀ alkylidenes), aralkyl (preferably C₆-C₃₀ aralkyls,more preferably C₆-C₁₈ aralkyls), cycloalkyl (preferably C₃-C₃₀cycloalkyls, more preferably C₃-C₁₈ cycloalkyls), ether, acetyl,aromatic, ester, hydroxy, alkoxy, cyano, amide, imide, andsilyl-substituted derivatives. Particularly preferred cyclic-olefins foruse in the present invention include those chosen from

and combinations of the foregoing, where each R³ and R⁴ is independentlychosen from H, and alkyl groups (preferably C₁-C₂₀ alkyls, morepreferably C₁-C₁₀ alkyls), and each R⁵ is independently chosen from H,substituted and unsubstituted aryl groups (preferably C₆-C₁₈ aryls),alkyl groups (preferably C₁-C₂₀ alkyls, more preferably C₁-C₁₀ alkyls),cycloalkyl groups (preferably C₃-C₃₀ cycloalkyl groups, more preferablyC₃-C₁₈ cycloalkyl groups), aralkyl groups (preferably C₆-C₃₀ aralkyls,more preferably C₆-C₁₈ aralkyl groups such as benzyl, phenethyl,phenylpropyl, and the like), ester groups, ether groups, acetyl groups,alcohols (preferably C₁-C₁₀ alcohols), aldehyde groups, ketones,nitriles, and combinations thereof.

Preferred acyclic olefins are chosen from branched and unbranched C₂-C₂₀alkenes (preferably C₂-C₁₀ alkenes). More preferably, the acyclicolefins have the structure (R⁶)₂C═C(R⁶)₂, where each R⁶ is independentlychosen from H and alkyl groups (preferably C₁-C₂₀ alkyls, morepreferably C₁-C₁₀ alkyls). Particularly preferred acyclic olefins foruse in the present invention include those chosen from ethene, propene,and butene, with ethene being the most preferred.

Methods of producing cyclic-olefin copolymers are known in the art. Forexample, cyclic-olefin copolymers can be produced by chainpolymerization of a cyclic monomer with an acyclic monomer. Whennorbornene is reacted with ethene under such conditions, anethene-norbornene copolymer containing alternating norbornanediyl andethylene units is obtained. Examples of copolymers produced by thismethod include those available under the TOPAS™ (available from TopasAdvanced Polymers) and APEL™ (produced by Mitsui Chemicals) brands. Asuitable method for making these copolymers is disclosed in U.S. Pat.No. 6,008,298. Cycloolefin copolymers can also be produced byring-opening metathesis polymerization of various cyclic monomersfollowed by hydrogenation. The polymers resulting from this type ofpolymerization can be thought of conceptually as a copolymer of etheneand a cyclic-olefin monomer (such as alternating units of ethylene andcyclopentane-1,3-diyl). Examples of copolymers produced by thisring-opening method include those provided under the ZEONOR™ (from ZeonChemicals) and ARTON™ (from JSR Corporation) brands. A suitable methodof making these copolymers by this ring-opening method is disclosed inU.S. Pat. No. 5,191,026.

Arylcyclobutene oligomers are well-known in the art. Suitablearylcyclobutene oligomers include, but are not limited to, those havingthe formula:

wherein B is a n-valent linking group; Ar is a polyvalent aryl group andthe carbon atoms of the cyclobutene ring are bonded to adjacent carbonatoms on the same aromatic ring of Ar; m is an integer of 1 or more; nis an integer of 1 or more; and R⁷ is a monovalent group. Preferably,the polyvalent aryl group, Ar, may be composed of 1-3 aromaticcarbocyclic or heteroaromatic rings. It is preferred that the aryl groupcomprise a single aromatic ring, and more preferably a phenyl ring. Thearyl group is optionally substituted with 1 to 3 groups chosen from(C₁-C₆)alkyl, tri(C₁-C₆)alkylsilyl, (C₁-C₆)alkoxy, and halo, preferablywith one or more of (C₁-C₆)alkyl, tri(C₁-C₃)alkylsilyl, (C₁-C₃)alkoxy,and chloro, and more preferably with one or more of (C₁-C₃)alkyl,tri(C₁-C₃)alkylsilyl, and (C₁-C₃)alkoxy. It is preferred that the arylgroup is unsubstituted. It is preferred that n=1 or 2, and morepreferably n=1. Preferably, m=1-4, more preferably m=2-4, and yet morepreferably m=2. It is preferred that R⁷ is chosen from H and(C₁-C₆)alkyl, and more preferably from H and (C₁-C₃)alkyl. Preferably, Bcomprises one or more carbon-carbon double bonds (ethylenicunsaturation). Suitable single valent B groups preferably have theformula —[C(R⁸)═CR⁹]_(x)Z¹, wherein R⁸ and R⁹ are independently chosenfrom hydrogen, (C₁-C₆)alkyl, and aryl; Z¹ is chosen from hydrogen,(C₁-C₆)alkyl, aryl, siloxanyl, —CO₂R¹⁰; each R¹⁰ is independently chosenfrom H, (C₁-C₆)alkyl, aryl, aralkyl, and alkaryl; and x=1 or 2.Preferably, R⁸ and R⁹ are independently chosen from H, (C₁-C₃)alkyl, andaryl, and more preferably H and (C₁-C₃)alkyl. It is preferred that R¹⁰is (C₁-C₃)alkyl, aryl, and aralkyl. Z¹ is preferably siloxyl. Preferredsiloxyl groups have the formula —[Si(R¹¹)₂—O]p-Si(R¹¹)₂—, wherein eachR¹¹ is independently chosen from H, (C₁-C₆)alkyl, aryl, aralkyl, andalkaryl; and p is an integer from 1 or more. It is preferred that R¹¹ ischosen from (C₁-C₃)alkyl, aryl, and aralkyl. Suitable aralkyl groupsinclude benzyl, phenethyl and phenylpropyl.

Preferably, the arylcyclobutene oligomers comprise one or more oligomersof the formula:

wherein each R¹² is independently chosen from H and (C₁-C₆)alkyl, andpreferably from H and (C₁-C₃)alkyl; each R¹³ is independently chosenfrom (C₁-C₆)alkyl, tri(C₁-C₆)alkylsilyl, (C₁-C₆)alkoxy, and halo; eachR¹⁴ is independently a divalent, ethylenically unsaturated organicgroup; each R¹⁵ is independently chosen from H, (C₁-C₆)alkyl, aralkyland phenyl; p is an integer from 1 or more; and q is an integer from0-3. Each R¹² is preferably independently chosen from H and(C₁-C₃)alkyl, and more preferably each R¹² is H. It is preferred thateach R¹³ is independently chosen from (C₁-C₆)alkyl,tri(C₁-C₃)alkylsilyl, (C₁-C₃)alkoxy, and chloro, and more preferablyfrom (C₁-C₃)alkyl, tri(C₁-C₃)alkylsilyl, and (C₁-C₃)alkoxy. Preferably,each R¹⁴ is independently chosen from a (C₂-C₆)alkenyl, and morepreferably each R¹⁴ is —CH═CH—. Each R¹⁵ is preferably chosen from(C₁-C₃)alkyl, and more preferably each R¹⁵ is methyl. Preferably, p=1-5,more preferably p=1-3, and yet more preferably p=1. It is preferred thatq=0. A particularly preferred arylcyclobutene oligomer,1,3-bis(2-bicyclo[4.2.0]octa-1,3,5-trien-3-yl ethenyl)-1,1,3,3tetramethyldisiloxane (“DVS-bisBCB”), has the formula

Arylcyclobutene oligomers may be prepared by any suitable means, such asthose described in U.S. Pat. Nos. 4,812,588; 5,136,069; 5,138,081; andInt. Pat. App. No. WO 94/25903. Suitable arylcyclobutene oligomers arealso commercially available under the CYCLOTENE™ brand, available fromDow Electronic Materials. The arylcyclobutene oligomers may be used asis, or may be further purified by any suitable means.

Vinyl aromatic oligomers are well-known in the art. Such vinyl aromaticoligomers include oligomers of only vinyl aromatic monomers andoligomers of vinyl aromatic monomers with one or more reactiveethylenically unsaturated co-monomers. Preferably, the vinyl aromaticmonomers contain one vinyl group. Suitable vinyl aromatic monomers areunsubstituted vinyl aromatic monomers and substituted vinyl aromaticmonomers where one or more hydrogens are replaced with a substituentgroup selected from the group of (C₁-C₆)alkyl, (C₁-C₆)alkoxy, halo, andamino. Exemplary vinyl aromatic monomers include, without limitation,styrene, vinyltoluene, vinylxylene, vinylanisole, vinyldimethoxybenzene,vinylaniline, halostyrene such as fluorostyrene, α-methylstyrene,β-methoxystyrene, ethylvinylbenzene, vinylpyridines, vinylimidazoles,vinylpyrroles, and mixtures thereof. Preferred vinyl aromatic monomersare styrene, vinyltoluene, vinylxylene, vinylanisole, ethylvinylbenzene,and mixtures thereof. Preferred reactive co-monomers are thosecomprising a reactive moiety, that is, a moiety capable of furtherpolymerization (or crosslinking) following formation of the vinylaromatic oligomer, such as an allyl moiety or a vinyl group, in additionto an olefinic (or ethylenically unsaturated) moiety used to for thevinyl aromatic oligomer. More preferably, the reactive co-monomerscomprise an allyl moiety in addition to the ethylenic unsaturation usedto form the vinyl aromatic oligomer, and even more preferably comprisean allyl ester moiety in addition to the ethylenic unsaturation.Exemplary reactive co-monomers useful in forming the vinyl aromaticoligomers include, but are not limited to, vinylcyclohexene, vinylethers, asymmetrical dienes or trienes such as terpene monomers (e.g.limonene or myrcene), diallyl maleate, allyl acrylate, allylmethacrylate, allyl cinnamate, diallyl fumerate, allyl tiglate,divinylbenzene, and mixtures thereof. Preferred reactive co-monomers arediallyl maleate, allyl acrylate, allyl methacrylate allyl cinnamate,allyl fumerate, and mixtures thereof, and more preferably diallylmaleate, allyl methacrylate and mixtures thereof. It will be appreciatedby those skilled in the art that one or more secondary co-monomers mayalso be used to form the vinyl aromatic oligomers. Such secondaryco-monomers are ethylenically unsaturated, but do not contain a reactivemoiety. Exemplary secondary co-monomers include, but are not limited to,(meth)acrylic acid, (meth)acrylamides, (C₁-C₁₀)alkyl (meth)acrylates,aromatic (meth)acrylates, substituted ethylene monomers, andpoly(alkylene oxide) monomers.

The molar ratio of vinyl aromatic monomers to co-monomers in such vinylaromatic oligomers is preferably from 99:1 to 1:99, more preferably from95:5 to 5:95, and still more preferably from 90:10 to 10:90. Such vinylaromatic oligomers may be prepared by any suitable method, such as anyof those known in the art. Typically, vinyl aromatic oligomers areprepared by free-radical polymerization of a vinyl aromatic monomer anda co-monomer. Preferred vinyl aromatic oligomers comprise unreactedallyl moieties that allow such oligomers to further cure.

The coating compositions are prepared by combining one or more oligomersas described above with one or more organic solvents, and one or moreoptional components. It is preferred that the oligomer is anarylcyclobutene oligomer. Suitable organic solvents include thosedescribed above for use in the adhesion promoter compositions. Exemplaryoptional components in the coating compositions include one or morecuring agents, one or more anti-oxidants, and the like. Curing agentsmay aid in the curing of the oligomers, and may be activated by heat orlight. Suitable curing agents include thermally generated initiators andphotoinitiators. The selection of such curing agents is well within theability of those skilled in the art. The amount of the oligomers,solvents and optional components in the coating composition may varyacross a wide range and is within the ability of one skilled in the art.It will be appreciated by those skilled in the art that the solidscontent in the coating compositions may be adjusted, along with the spinspeed, to achieve a desired thickness of the coating composition on theadhesion promoter treated surface.

The coating compositions may be disposed (or coated) on the adhesionpromoted device substrate surface by any suitable method, such as thosedescribed above for disposing the adhesion promoter on the devicesubstrate. Such methods of depositing coating compositions arewell-known in the art. After being disposed on an adhesion promotedsurface, the coating compositions are typically cured using theappropriate method for the oligomer selected. Such curing methods arewell-known in the art. For example, arylcyclobutene oligomers may becured by heating, or in the case of photodefinable arylcyclobuteneoligomers by exposure to actinic radiation (light) of an appropriatewavelength.

Also provided by the present invention is a self-priming coatingcomposition comprising a poly(alkoxysilane) hydrolyzed with ≦1 mole % ofwater, an oligomer chosen from polyarylene oligomers,poly(cyclic-olefin) oligomers, arylcyclobutene oligomers, vinyl aromaticoligomers, and mixtures thereof, and an organic solvent, wherein thecomposition comprises ≦1 mole % of alcohol of hydrolysis. Optionally,these self-priming compositions may comprise one or more additionalcomponents such as anti-oxidants, photo-cross-linking agents, andcoating enhancers. Such optional components are well-known to thoseskilled in the art. Any of the poly(alkoxysilanes) described above maybe used in this composition. Any of the oligomers described above forthe coating composition may be used in this self-priming composition,and preferably the oligomer is an arylcyclobutene oligomer. Suitableorganic solvents are those described above for use in the adhesionpromoter compositions. As used herein, the term “self-priming coatingcomposition” refers to a composition comprising both an adhesionpromoting poly(alkoxysilane) hydrolyzed with ≦1 mole % of water and acoating oligomer, and preferably also comprising an organic solvent. Anadvantage of these self-priming coating compositions is that a separatestep of applying an adhesion promoter can be avoided. Alternatively,these self-priming coating compositions may be used to form a firstlayer coating layer, upon which subsequent coating layers are deposited.In certain applications, the use of a self-priming coating compositionis preferred over the use of a separate adhesion promoter composition.Such self-priming compositions may suitably be used to form dielectriccoatings, photodefinable coatings, temporary adhesives, permanentadhesives, and the like.

The amounts of the poly(alkoxysilane) hydrolyzed with ≦1 mole % ofwater, coating oligomer, and solvent employed in the self-primingcoating composition depends upon a number of factors including thespecific end-use application and the properties desired. If theself-priming coating composition is intended to have one or more coatingoligomer layers subsequently applied to it, the self-priming coatingcomposition will typically contain lesser amounts of the coatingoligomer than when no subsequent coating oligomer layer is used. Ingeneral, regardless of its intended end-use, the self-priming coatingcomposition comprises from 0.01 to 10 wt % poly(alkoxysilane) hydrolyzedwith ≦1 mole % water, from 10 to 99.98 wt % solvent, and from 0.01 to 90wt % coating oligomer, where the weight percents are based on the totalweight of the composition. Preferably, the self-priming coatingcompositions comprise form 0.01 to 5 wt % of poly(alkoxysilane)hydrolyzed with ≦1 mole % of water, more preferably from 0.01 to 3 wt %,and even more preferably from 0.01 to 2 wt %. When subsequent coatingoligomer compositions will be disposed on the self-priming composition,it is preferred that the coating oligomers in the self-priming coatingcompositions are present in an amount of from 0.01, more preferably from1, and even more preferably from 2 wt % to 20, more preferably 10, andeven more preferably 5 wt %. When subsequent coating oligomercompositions will not be disposed on the self-priming coating, it ispreferred that the coating oligomer be present in the composition in anamount of from 5, more preferably from 10, and yet more preferably from20 wt % to 90, more preferably to 80, and still more preferably to 65 wt%. Preferred amounts of solvent vary from 10 to 98 wt %, more preferablyfrom 20 to 90 wt %, and still more preferably from 20 to 75 wt %. In oneembodiment, the composition comprises from 0.01 to 10 wt % ofpoly(alkoxysilane) hydrolyzed with ≦1 mole % water, from 40 to 99.5 wt %of solvent; and from 1 to 80 wt % of coating oligomer, based on thetotal weight of the composition; wherein the composition comprises ≦1mole % of alcohol of hydrolysis. In another embodiment, the compositioncomprises from 0.01 to 10 wt % of poly(alkoxysilane) hydrolyzed with ≦1mole % of water, from 10 to 99.9 weight percent of solvent, and from0.01 to 90 percent by weight of coating oligomer, based on the totalweight of the composition wherein the composition comprises ≦1 mole % ofalcohol of hydrolysis.

The self-priming coating compositions may be disposed on a devicesubstrate to form a coated film using any of the methods described abovefor the adhesion promoting compositions. Spin-coating is a preferredmethod. Following deposition on a device substrate, the coated film istypically cured, such as by heating, exposure to actinic radiation(light), or a combination thereof. Photodefineable arylcyclobutenes aretypically photocrosslinked prior to further cure. The specific curingconditions used depend on the particular oligomer selected, theparticular application such as whether the coated film is a dielectricor an adhesive, as well as on other parameters known to those skilled inthe art.

Dynamic light scattering is a technique for determining the sizedistribution profile of small particles in a suspension and can be usedas a facile method to monitor the degree of hydrolysis of alkoxysilanes.Conventional hydrolysis of alkoxysilane adhesion promoters, particularlyuncontrolled hydrolysis, leads to formation of components in thecomposition having mean particle sizes>>2 nm as determined by dynamiclight scattering, and typically such components have mean particlesizes >10 nm. The low level of hydrolysis of the poly(alkoxysilanes) ofthe present invention results in components having mean particlesizes<<10 nm, typically ≦2 nm, and preferably ≦1 nm, as determined byconventional dynamic light scattering techniques. Preferably, thepresent poly(alkoxysilanes) hydrolyzed with ≦1 mole % water have a meanparticle size of ≦2 nm, and more preferably ≦1 nm. It is also preferredthat the present compositions have a unimodal particle sizedistribution. Hydrolyzed alkoxysilanes having a mean particle sizedistribution of >1 nm do not provide adequate adhesion for manyapplications, such as when used with imageable dielectrics.

EXAMPLE 1

Bis[3-(trimethoxysilyl)propyl]amine (0.41 g), of[3-(2-aminoethylamino)propyl]-trimethoxysilane (0.21 g), and 99.38 g of4-methyl-2-pentanol containing 400 ppm water were combined in a 200 mLbottle. The mixture was stirred with a magnetic stirrer at ambienttemperature (23° C.) in order to effect hydrolysis. Hydrolysis proceededsuch that a single phase solution is produced in 15 minutes.

COMPARATIVE EXAMPLE 1

Vinyltrimethoxysilane (0.3 g) and 99.7 g of 1-methoxy-2-propanolcontaining 800 ppm water were combined in a 200 ml bottle. The mixturewas stirred using a magnetic stirrer at ambient temperature (23° C.) inorder to effect hydrolysis. Hydrolysis proceeded such that a singlephase solution was produced in 15 minutes.

COMPARATIVE EXAMPLE 2

3-Aminopropyltriethoxylsilane (0.1 g) and 99.9 g of 1-Methoxy-2-propanolcontaining 800 ppm water were combined in a 200 mL bottle. The mixtureis stirred magnetically at ambient temperature (23° C.) in order toeffect hydrolysis. Hydrolysis proceeded such that a single phasesolution was produced in 15 minutes.

COMPARATIVE EXAMPLE 3

[3-(2-Aminoethylamino)propyl]trimethoxysilane (0.6 g) and 99.4 g of1-methoxy-2-propanol containing 800 ppm water were combined in a 200 mLbottle. The mixture was stirred using a magnetic stirrer at ambienttemperature (23° C.) in order to effect hydrolysis. Hydrolysis proceededsuch that a single phase solution was produced in 15 minutes.

EXAMPLE 2

Bis[3-(trimethoxysilyl)propyl]amine (0.6 g), and 99.4 g of4-methyl-2-pentanol containing 400 ppm waterwere combined in a 200 mLbottle. The mixture was stirred using a magnetic stirrer at ambienttemperature (23° C.) in order to effect hydrolysis. Hydrolysis proceededsuch that a single phase solution was produced in 15 minutes.

EXAMPLE 3

Bis[3-(triethoxysilyl)propyl]amine (0.5 g) and 99.5% of4-methyl-2-pentanol containing 400 ppm water were combined in a 200 mLbottle. The mixture was stirred using a magnetic stirrer at ambienttemperature (23° C.) in order to effect hydrolysis. Hydrolysis proceededsuch that a single phase solution was produced in 15 minutes.

EXAMPLE 4

Bis[3-(triethoxysilyl)propyl]amine (0.5 g) and 99.5% of1-methoxy-2-propanol containing 800 ppm water were combined in a 200 mLbottle. The mixture was stirred using a magnetic stirrer at ambienttemperature (23° C.) in order to effect hydrolysis. Hydrolysis proceededsuch that a single phase solution was produced in 15 minutes.

EXAMPLE 5

Benzocyclobutene bis(3-(triethoxylsilyl)propyl)acrylamide (0.5 g) and99.5 g of 1-methoxy-2-propanol containing 500 ppm water were combined ina 200 mL bottle. The mixture was stirred using a magnetic stirrer atambient temperature (23° C.) in order to effect hydrolysis. Hydrolysisproceeded such that a single phase solution was produced in 15 minutes.

EXAMPLE 6

N¹,N¹-Bis(3-(trimethoxysilyl)propyl)ethane-1,2-diamine (0.5 g) iscombined with 2-methyl-1-butanol containing 350 ppm water in a 200 mLbottle. The mixture is stirred at ambient temperature (23° C.) in orderto effect hydrolysis.

EXAMPLE 7

To a 200 mL bottle are combined 4 methyl-2-pentanol containing 250 ppmwater and3-(trimethoxysilyl)-N-(2-(trimethyoxysilyl)ethyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine.The mixture is stirred at ambient temperature (23° C.) in order toeffect hydrolysis.

EXAMPLE 8

To a 200 mL bottle are combined 4 methyl-2-pentanol containing 400 ppmwater andbis(3,3,9,9-tetramethoxy-2,10-dioxa-3,9-disilaundecan-6-yl)amine. Themixture is stirred at ambient temperature (23° C.) in order to effecthydrolysis.

EXAMPLE 9

The adhesion promoting compositions from Examples 1-5 and ComparativeExamples 1-3 were evaluated using a lithographic printing adhesion test.Each adhesion promoter composition was coated on a 200 mm test waferusing a Site Trac TT5-XP coater at a spin speed of 2000 rpm for 40seconds followed by a 90° C. bake for 90 seconds to ensure solventremoval. An oligomer composition comprising 40% of an aqueousdevelopable benzocyclobutene oligomer, which is a copolymer ofDVS-bisBCB and benzocyclobutene acrylic acid having a molecular weightof approximately 5000, in a mixture of PROGLYDE™ DMM, PGMEA and anisoleand containing a trifunctional diazonapthoquinone photoactive compound(CYCLOTENE™ P6505, available from The Dow Chemical Company, Midland,Mich.) was coated on top of the adhesion promoter layer using a SiteTrace TT6-XP coater at a spin speed around 1500 rpm to target a filmthickness of approximately 6.5 μm. The oligomer composition was nextedbaked at 90° C. for 90 seconds to ensure solvent removal. Next, eacholigomer-coated wafer was exposed on an ASML 200 i-line stepper using abright field reticle to print rows of variously sized posts (from 1 to25 μm) on the wafer. After exposure, a 15 minute post exposure hold wasutilized to allow moisture diffusion back into the film. Next, theexposed areas of the oligomer resin were developed on a Site Trac TTP-X5tool using a CD-26 developer solution employing a 60 second singlepuddle followed by a 90 second de-ionized water rinse. The post patternremaining on the wafer was evaluated under an optical microscope. Asample was considered to pass the lithographic adhesion test when theminimum feature size of the remaining posts after development was lessthan or equal to 5 μm. The data are reported in Table 1 below.

EXAMPLE 10

Dynamic light scattering measurements were carried out using a MalvernZetasizer Nano ZS instrument. A sample of an adhesion promoter solution(1.5 mL) was transferred to a quartz cuvette, and then the cuvette wasinserted in the sample holder of the Zetasizer instrument. Theinstrument software was set up for size measurement, and 15 to 24 scanswere normally required to obtain an accurate particle size distributionfor each sample. The mean particle sizes determined for Examples 1-5 andComparative Examples 1-3 are reported in Table 1 below. Each of theadhesion promoters of the invention had only a single peak (unimodaldistribution) with a mean particle size of <1 nm. Each of thecomparative examples had at least one peak with a mean particle size >1nm. Comparative Example 1 had 2 peaks (bimodal distribution), with onedistribution having a mean particle size of >10 nm. Such large meanparticle sizes in the comparative examples indicates the formation oflarger nanoparticles due to the larger amount of silane hydrolysis, ascompared to the poly(alkoxysilanes) of the invention.

TABLE 1 Lithographic Printing Adhesion to Adhesion Test - Post MeanParticle Size Formulation silicon Size Remaining (μm) (nm) ComparativePoor No posts remaining <1, >10 Example 1 bimodal Comparative Poor Noposts remaining 3-5 Example 2 Comparative Poor 15  >1 Example 3 Example1 Good 3 <1 Example 2 Good 3 <1 Example 3 Good 2 <1 Example 4 Good 2 <1Example 5 Good 2 <1

EXAMPLE 11

The adhesion promoting compositions from Examples 1-5 and ComparativeExamples 1-3 were evaluated according to the Cross-Hatch/Tape Peel test(ASTM D 3359) using a PA-2000 kit from Gardco. The cross hatch wasapplied and excess debris removed using a steady stream of compresseddry air prior to tape peel. After tape peel, the adhesion was evaluatedand each of the adhesion promoting compositions from Examples 1-5 andComparative Examples 1-3 were found to pass with 0% removed.

EXAMPLE 12

A temporary bonding coating composition was prepared by combining 83.63g of 68.5% DVS-bisBCB oligomer (having an average molecular weight of25,000-30,000) in Proglyde™ DMM solvent was added 8.78 g ofpoly(tetramethylene glycol) having a molecular weight of 2900,(available as PolyTHF 2900, from BASF), 4.17 g of BAC-45 (a diacrylateterminated butadiene rubber having a molecular weight of 3000), 0.68 gof dicumyl peroxide, 0.49 g of a commercial antioxidant, and 2.25 g ofProglyde™ DMM solvent. The composition was manually mixed with a woodenstick, heated to 50° C. for approximately 1 hour, and then rolled untilhomogeneous.

200 mm silicon wafers were subjected to an oxygen plasma etch for 10seconds. Next, 2 mL of the adhesion promoter from Example 4 was spincoated on the attachment surface of a carrier wafer (2000 rpm, 30seconds), followed by a soft bake at 120° C. for 90 seconds, followed bycooling. The temporary bonding coating composition was spin coated (2000rpm) on a device wafer, soft baked at 120° C. for 90 seconds, cooled for30 seconds, and soft baked at 160° C. for 120 seconds to form a layer ofa temporary bonding composition on the device wafer. The carrier waferwas then vacuum laminated to the temporary bonding coating compositionat 80° C. for 60 seconds, with vacuum applied for 45 seconds andpressure applied for 60 seconds. The laminated wafers were then cured byheating on a hot plate, device side down, for 120 seconds at 210° C., ina nitrogen atmosphere. The thickness of the cured temporary bondinglayer was approximately 25 μm. Following curing, the wafers weresuccessfully debonded with a razor blade inserted near a notch andguided around the wafer, with the device wafer separating from thetemporary bonding composition. The temporary bonding compositionremained adhered to the adhesion promoted attachment surface of thecarrier wafer.

EXAMPLE 13

The procedure of Example 12 was repeated except that the temporarybonding coating composition also contained 41.82 g of a 90/10styrene:diallyl maleate oligomer. The coating composition containedDVS-bisBCB oligomer and styrene:diallyl maleate oligomer in a weightratio of 1:1. The thickness of the cured temporary bonding layer fromthis composition was approximately 26 μm. Following curing, the waferswere successfully debonded with a razor blade inserted near a notch andguided around the wafer, with the device wafer separating from thetemporary bonding composition. The temporary bonding compositionremained adhered to the adhesion promoted attachment surface of thecarrier wafer.

EXAMPLE 14

The procedure of Example 12 was repeated except that the DVS-bisBCBoligomer was replaced with 83.63 g of a 90/10 styrene:diallyl maleateoligomer in Proglyde™ DMM solvent (68.5% solids). This coatingcomposition contained no DVS-bisBCB oligomer. The thickness of the curedtemporary bonding layer from this composition was approximately 36 μm.Following curing, the wafers were successfully debonded with a razorblade inserted near a notch and guided around the wafer, with the devicewafer separating from the temporary bonding composition. The temporarybonding composition remained adhered to the adhesion promoted attachmentsurface of the carrier wafer.

What is claimed is:
 1. A composition comprising: an oligomer chosen frompolyarylene oligomers, poly(cyclic-olefin) oligomers, arylcyclobuteneoligomers, vinyl aromatic oligomers, and mixtures thereof; apoly(alkoxysilane) hydrolyzed with ≦1 mole % of water; and a solvent;wherein the composition comprises ≦1 mole % of alcohol of hydrolysis andwherein the poly(alkoxysilane) has from 2 to 6 alkoxysilane moieties. 2.The composition of claim 1 wherein the poly(alkoxysilane) is hydrolyzedwith ≦0.5 mole % of water.
 3. The composition of claim 1 wherein thepoly(alkoxysilne) prior to being hydrolyzed has the formula:

wherein each R is independently chosen from (C₁-C₆)alkylidene,(C₁-C₆)alkylene, (C₆-C₁₀)arylene, and (C₂-C₆)alkenylene; each R¹ isindependently chosen from H, (C₁-C₆)alkyl and (C₁-C₆)acyl; each Z isindependently chosen from (C₁-C₆)alkyl, (C₂-C₆)alkenyl and —OR¹;X═(C₆-C₁₀)arylene, N(Y) or a covalent bond; Y═H, (C₁-C₆)alkyl,(C₁-C₆)alkylene-N(Y¹)₂, (C₂-C₆)alkenyl, (C₁-C₆)alkylene-Si(Z)₂(OR¹), oraryl(meth)acryloyl; and Y¹═H, (C₁-C₆)alkyl, or (C₂-C₆)alkenyl; whereineach R is optionally substituted with one or more of(C₁-C₆)alkylidene-Si(Z)₂(OR¹) and (C₁-C₆)alkylene-Si(Z)₂(OR¹).
 4. Thecomposition of claim 1 wherein the arylcyclobutane oligomer has theformula:

wherein B is a n-valent linking group; Ar is a polyvalent aryl group andthe carbon atoms of the cyclobutene ring are bonded to adjacent carbonatoms on the same aromatic ring of Ar; m is an integer of 1 or more; nis an integer of 1 or more; and R⁵ is a monovalent group.
 5. Thecomposition of claim 1 having a mean particle size of ≦1 nm asdetermined by dynamic light scattering.
 6. The composition of claim 1wherein the oligomer is an arylcyclobutene oligomer.
 7. A process formanufacturing a device, comprising: providing a device substrate havinga surface to be coated; disposing a coating of the compositioncomprising: an oligomer chosen from polyarylene oligomers,poly(cyclic-olefin) oligomers, arylcyclobutene oligomers, vinyl aromaticoligomers, and mixtures thereof; a poly(alkoxysilane) hydrolyzed with ≦1mole % of water; and a solvent; wherein the composition comprises ≦1mole % of alcohol of hydrolysis and wherein the poly(alkoxysilane) hasfrom 2 to 6 alkoxysilane moieties on the substrate surface; and curingthe coating.
 8. The process of claim 7 wherein the device substrate isan electronic device substrate.
 9. The process of claim 8 wherein theelectronic device substrate comprises a surface comprising one or moreof silicon, glass, ceramic, and metal.
 10. The process of claim 7wherein the poly(alkoxysilane) prior to being hydrolyzed has theformula:

wherein each R is independently chosen from (C₁-C₆)alkylidene,(C₁-C₆)alkylene, (C₆-C₁₀)arylene, and (C₂-C₆)alkenylene; each R¹ isindependently chosen from H, (C₁-C₆)alkyl and (C₁-C₆)acyl; each Z isindependently chosen from (C₁-C₆)alkyl, (C₂-C₆)alkenyl and —OR¹;X═(C₆-C₁₀)arylene, O, S, S—S, S—S—S, S—S—S—S, N(Y), P(Y), or a covalentbond; Y═H, (C₁-C₆)alkyl, (C₁-C₆)alkylene-N(Y¹)₂, (C₂-C₆)alkenyl,(C₁-C₆)alkylene-Si(Z)₂(OR¹), or aryl(meth)acryloyl; and Y¹═H,(C₁-C₆)alkyl, or (C₂-C₆)alkenyl; wherein each R is optionallysubstituted with one or more of (C₁-C₆)alkylidene-Si(Z)₂(OR¹) and(C₁-C₆)alkylene-Si(Z)₂(OR¹).
 11. The process of claim 7 wherein theoligomer is an arylcyclobutene oligomer.
 12. The process of claim 11wherein the arylcyclobutane oligomer has the formula:

wherein B is a n-valent linking group; Ar is a polyvalent aryl group andthe carbon atoms of the cyclobutene ring are bonded to adjacent carbonatoms on the same aromatic ring of Ar; m is an integer of 1 or more; nis an integer of 1 or more; and R⁵ is a monovalent group.
 13. Theprocess of claim 7 wherein the adhesion promoting composition has a meanparticle size of ≦1 nm, as determined by dynamic light scattering.